铵离子对3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)硝解反应影响（英文）  

Influence of Ammonium Ion on Nitrolysis of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane(DPT)

作　　者：黄晓川[1] 尉涛[1] 邱少君[1] 郭涛[1] 唐望[1] 葛忠学[1] 孟子晖[2] 徐志斌[2] 

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]北京理工大学化工与环境学院应用化学系,北京100081

出　　处：《含能材料》2015年第11期1151-1154,共4页Chinese Journal of Energetic Materials

摘　　要：基于3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)在HNO3-N H4N O3及HNO3中两种硝解机理,分别通过实验和理论计算方法对NH+4在DPT硝解反应中的作用进行了研究。将三种不同的铵盐(NH4)2H PO4,(NH4)2SO4和CH3C O O N H4添加到硝解体系中,考察了NH+4对HM X产率的影响。结果表明,与NH4N O3的作用相似,以上三种铵盐可提高HM X产率,提高率分别为41.5%、37.4%和20.7%。在不同的HNO3-铵盐体系中,当N H+4与DPT的摩尔比接近10时,HM X的产率均达到最大值,分别为56.3%、52.2%和35.5%。对比了HNO3-铵盐和H N O3-硝酸盐体系中D PT硝解反应的结果,发现N H+4对HM X产率的提高起主导作用。采用密度泛函理论(DFT)对NH+4在DPT硝解反应过程中的作用机理进行了理论解释,得出HNO3/N H+4体系中D PT硝解反应的活化能为133.95 k J·m ol-1,低于HNO3体系中的376.73 k J·mol-1。Based on the two mechanisms of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3 ,1]nonane （DPT） nitrolysis via HNO3-NH4 NO3 or HNO3 , the effects of NH： in nitrolysis of DPT were studied by experiment and theoretical calculation. The effect of NH4＋on the yield of HMX was studied with adding the ammonium salts including （NH4）2HPO4, （NH4）2SO4 and CH3COONH4 to nitrate solution system. Results show that the above-men- tioned ammonium salts can improve the yield of HMX to 41.5%, 37.4% and 20.7%, respectively. Their function is similar to NH4 NO3. In differ- ent nitric acid-ammonium salt systems, when the molar ratio of NH4＋ and DPT is close to10, the yield of HMX reaches a maximum value of 56.3%, 52.2% and 35.5%, respectively. Results of the nitrolysis of DPT in nitric acid-ammonium salt systems and nitric acid-nitrate system are compared, finding that NH： plays a dominant role in improving the yield of HMX. The reaction mechanism of NH： in the nitrolysis process of DPT is theoretical- ly explained by the density functional theory （ DFT）, deriving that the activation energy of DPT nitrolysis in HNO3 INH~ is 133.95 kJ · mol-1 , lower than 376.73 kJ· mol-1 in HNO3.

关 键 词：1 3 5 7-四硝基-1 3 5 7-四氮杂环辛烷 3 7-二硝基-1 3 5 7-四氮杂双环[3.3.1]壬烷(DPT) 硝酸铵 硝化 密度泛函理论(DFT) 反应机理 

分 类 号：TQ560.1[化学工程—炸药化工]